Fume disposal in catalyst regeneration systems



Jan! 5, 1943- G. s. DUNHAM FUME DISPOSAL IN CATALYST REGENERATION SYSTEMS Filed Oct. l, 1938 msk IVY

. km, Now. h FSQ INVE A Su nu Patented Jan. 5, 1943 UNITED .STATES FUME DISPOSAL IN CATALYST REGENEBATION SYSTEMS George S. Dunham, Ardmore, Pa., assignor to Snoopy-Vacuum Oil Company, Incorporated, New York, N- Y.. a corporation of. New York Application october 1, 193s. .serai Nasse-13s i 1 Claim. l( Cl. 23288) This invention has to do with the problem o! disposal and utilization of fume from there- --generation, by combustion, oi spent contact masses.

Known processes for the conversion o! hydro carbons consist of passing the hydrocarbons. in vapor form, at reaction or conversion temperatures through a contact mass capable of catalyzing the desired conversion. The desired reaction occurs in the presence of the contact mass and is accompanied by the' deposit on and in the contact mass of a combustible mater-lai of carbonaceous nature. After a period of time, the' carbonaceous deposit builds up sumciently to impair the activity of the catalytic contact mass,

and Vit must beremoved. The usual method o! removal is by a regeneration in situ of the contact mass, accomplished by passing a combustion supporting gas, such as air. through the contact vention is specically concerned with the prob-- lem of disposal and utilization of such fuma The principal object or this invention is the provision oi a process whereby such waste gases from regeneration may be disposed oi convert iently, under efcient control. and in which s.

proper utilization and recovery oi energy otherposting gas. 'such as air, therethrough to burn oil! I the contaminant.l

Catalyst case I is equipped with valves 2 an l for the entrance and exit, respectively, of hvdrocarbons during reaction, and with valves 4 and I for the entrance and exit, respectively. of regeneration medium during regeneration. Dur'- ing the operation here discussed, valves 2 andl are closed, 4 and l being Open.- regeneration me- "10 dium, in this' ease air. lssupplied by pipe i and the nue gas `or fume from regeneration is removed through pipe l. To maintain regenerative combustion at anpemcie'nt level, it is necessary 4 lto preheat the air enteringthrough piped* Inv S15 the prior art over which this invention is animprovement, thispreheating is accomplished by passing the incoming air through tubes in a sepi arately red furnace or stove. The "iume leav v ing through pipe l contains a substantial quani mass, and burning ot! the deposit. The tume" "20 tity of 'carbon monoxide, some hydrocarbon vola- -or exit gases from such a regeneration are odorous, and, because `o! the presence of hydrocab' tilized from the contaminant in Land' 'a substantial amount ot unconsumed oxygen. jUnder proper conditions it is still combustible, or may be made so by the introduction of some air. It

'251s also odorous. These considerations require further treatment before discharge to atmosphere, and it is customary to ellect such treat-' ment by leading the gases or lume from' pipe T-,

through a combustion case I containing a com- 'so bastion catalyst l, mpportec by a grid it. combustible fume further burns in caael'bya process of surface combustion or the likejwithin wise wasted is possible. A further principm o'n-', 1the mmis 0f ma mbustmn wmf* is the provision of apparatus the i which may me any fom ppmpm for te disclosed process may be accomplished. other 35 action but is conveniently composed ot small pel'- objects are in part obvious or may be mentioned j )3 5-' mames t a clay'uke mmmrimmt' hereinafter. me? with an oauon um 'as' un e t @or examp e, copper o e.v v 5 f: segnatamente i, dem am we am Y 40 pipe "fand it is further customary to recover at specication, the single ligure oi which is a div agrammatic representation of apparatus s uililes a' portion -of the energy present m y cient for accomplishment ofthe process. g, mi, them to e!" In the drawing l represents a catalyst case if wthrrgtmaesu; pump containing contact mass which has been contam- 5 'uc A; pump u ,anche 'I inated as hereinbeioie described. and which ls drive me electric 'mater mud 1% com ma* being regenerated. Il', 1S t0 undel'tod that an. for muon which' is discharged the catalyst case I has nopart'in the present V pipe 't The uhm-hm mme entering case g has process 0121161* than being `the lll' 0f the s tempemture of about 850e" F mmm and fume 'It is also to be understood that this '5o may be higher. After the mmy exothrmic Catalyst CaSe i is merely l'epi'selltative 0f Illy .Ata the absence catalyst case, being regenerated after any prccof mmm be qui@ high, The gas-tm. ess, wherein a contact mass has been contamimm; m @um me be expedtg temperatures nated by a carbonaceous deposit and which is beof greater aboutjco F. and consequently-it v ing regenerated by blowing a combustion suv- 55 is customarytobrins the temperature of the gases in pipe II below this by admixing cold air or by spraying in water at some point along pipe II. Also, the combustion catalyst in case 8 is usually adversely affected by temperatures of the order of 1100-1200 F. and to remain safely below such temperatures it is usually necessary to conduct the reaction in case 8 at a rate slower than that which would otherwise be possible.

To this process and structure of the prior art I have made certain additions and alterations.

For control of the temperature in case 8 I have arranged therein a series of tubes I1 and circulate a fluid heat exchange medium in such tubes. The arrangement of these tubes is such that every particle of contact mass in case 8 is in effective indirect heat exchange relationship with the heat exchange medium, so that contact mass temperature may be controlled accurately and suiiicient heat extracted to prevent damage to the contact mass While permitting the burning to take place at a maximum rate. This control serves also to control the temperature of the gases leaving through" pipe II without wasteful loss by the heating of an extraneous medium such as cold air or sprayed water. The heat exchange medium in pipe Il originates in hot well I8, from whence itis pumped by pump I9 through pipe 20 and to which it returns by pipe 2I.

To effectively utilize the heat thus removed from case 8 there is provided a heat exchanger 22 into which fresh air for regeneration ows from pipe I6 and from which the heated regeneration air is passed to pipe 6. For heating this air, pump 23 picks up hot heat exchange medium from hot well I8, delivering it through pipe 24 to tubes 25 in heat exchanger 22. 4The heat exchange medium is returned to hot well I8 by pipe 28. To control the degree of heating of the air, the pump 23 is provided with a variable speed drive, such as a steam turbine 21 controlled by a valve 28, which valve 28 vis opened or closed responsive to the temperature in pipe 8 observed by thermocouple 29, in known manner.

In case the heat removed from case 8 is in excess of the heat taken up in preheating regeneration air, as is frequently the case, an additional heat removal means is provided by heat exchanger 30, installed in pipe 26. Heat exchanger 3J may be used to heat water, to heat oil for the conversion or for some other process, or may take the form of a waste heat boiler. If preferred, heat exchanger 30 may be installed in pipe 20.

In most forms of conversion catalyst cases, such as case I, some provision is made for control of regeneration temperature and removal of heat by means of a heat exchange medium circulated in coil 3| placed in case I, these coils being fed heat exchange medium through pipe 32, which is removed through pipe 33. In such installations, the pipes 34 and 35 r'nay be provided, as well as valves 36, 31, 38, 39, 40', 4I in order that this heat exchange medium may also be used for regeneration air heating, for example duringv emergencies, or uwhen the heat supply from case 8 is vinsuflicient for air heating.

The heat exchange medium utilized herein should be one -possessed of low viscosity, low vapor pressure and high specific heat at the temperature encountered, viz. 600 F. to 1200o F. Low melting point metals and alloys and fused mixtures of inorganic salts may be used. Of these, the fused mixtures of inorganic salts are best, and an exemplary medium is a fused mixture of alkali salts of the oxy-acid of nitrogen.

.Cil

for complete control of the temperatures within case 8 and pipe II and at the same time eifectively provides for utilization of the energy developed in the fume and during fume disposal. It completely obviates former sources vof loss and poor control, and also does away with the necessity of maintaining a separate combustion in a separate stove or furnace for the preheating of regeneration medium.

As an example of operation according to this process and of the conditions encountered, the,

following may be cited.

The conversion case I, having previously contaminated in a vapor phase cracking operation, wherein hydrocarbon vapors were passed through case I at a temperature of 875 F. for a period of twenty minutes, during which there was deposited upon the contact mass in case I about 2% of its weight of carbonaceous material, is now being regenerated. This regeneration'is being accomplished by passing in air` through pipe 6, preheated to about 850 F. at such a rate 'V that the 2% of carbon will be removed during a period of about twenty minutes. The temperature of the contact mass in case I is controlled by circulating heat exchange medium at a temperature of about 875 F. through coils 3|.

In this case no heat exchange medium from case I passes through pipes 34 and 35. Fume leaving case I through pipe I is at a temperature of 875 F. to 900 F., and in passing through case 8 undergoes further combustion. Sufficient heat exchange medium is circulated through pipes I1 in case 8 to remove therefrom the heat of this combustion, the exit gases in pipe II being held to about 925 F. and the heat exchange medium being held within a temperature range of about S50-925 F. Sufficient heat exchange medium is circulated through heat exchanger 22 to bring the regeneration air to about 850u F., excess heat being removed from the system by heat exchanger 30.

In case only one or two catalyst cases such as I are operated in conjunction with a fume combustion case 8 the intensity of combustion in 8 will vary with the cycle, being highest when the fumes entering 8 are coming from a catalyst case I in the first state of regeneration. In such event, even though the amount of heat removed from case 8 per unit of time varies, the system disclosed is capable of effective action to maintain the desirable temperatures indicated.

It is to be understood that specific data set forth herein is given solely for purposes of illustration and that the inventiony is not limited thereto or thereby, but only by such limitations as are set forth in the appended claim.

.I claim:

In an apparatus for catalytic conversion of hydrocarbon oils by contact with a lsolid adsorptive catalyst at elevated temperature followed by regeneration of the catalyst by burning carbonaceous deposits therefrom with an oxidizing gas, said apparatus including a conversion chamber, a bed of said adsorptive catalyst in said conversion chamber, a first heat exchanger within said conversion chamber for conducting a heat exchange fluid in indirect heat exchange relai tion with said bed of adsorptive catalyst, means It may be seen that this operation provides a combustion chamber, a bed of combustion for conducting regeneration fume from said cony version chamber to and through said combustion chamber; the improvement which comprises a second heat exchanger in said combustion chamber, inlet means to supply a heat exchange uid to said second heat exchanger, outlet means to exhaust saduid from said second heat exchanger, a third heat exchanger in said preheater, means to conduct fluid from said outlet means to said third heat exchanger, a conduit to withdraw uid from said third heat exchanger, valved means for conducting iiuid from said conduit to said outlet means of said second heat exchanger to mingle with iiuid therein, a valve in said means to withdraw fluid from said first heat exchanger, valved means to conduct uid from said conduit to said means to withdraw fluid from said first -heat exchanger at a point therein on the side of said valve remote from said rst heat exchanger, means to conduct fluid to the inlet of said third heat exchanger from a point in said means to withdraw uid from said -first heat exchanger at a point therein inter- 

